CN101010183A - Method for making colored silicone hydrogel contact lenses - Google Patents

Abstract

The present invention generally relates to a method for making made-to-order (MTO) or customized silicone hydrogel lenses which have printed images on and/or below lens surfaces. A preferred method of the invention comprises printing and curing an ink on the molding surface of a mold for molding a single-side molded lens blank, producing the single-sided molded lens blank having a molded surface corresponding to one of the anterior and posterior surfaces of the lens to be produced and having an image embedded in the lens body and below lens surface, and directly lathing the lens blank on the side opposite to the molded surface to form the other lens surface. Colored silicone hydrogel lenses produced according to the invention will be useful as daily wear lenses and extended wear lenses. The lenses will allow alteration or enhancement of a patient's eye color.

Description

Make the method for colored silicone hydrogel contact lenses

Present invention relates in general to make the method for colored silicone hydrogel contact lenses.More particularly, the present invention relates to make the method for the colored silicone hydrogel contact lenses of special or customization.

Background technology

For the purpose of decorating, be dispersed in the lens or to be printed on the demand of contact lenses of the colouring agent on the lens very high for having one or more.These Tinted contact lenses have improved the natural beauty of eyes, or on wearer's iris, provide unique pattern, or provide non-decorative pattern or sign, as sign of rotation, counter-rotating sign, product/trade mark code, lot number, " DEMO " lens etc., this is of value to wearer, Eye Care teacher and manufacturing firm.

Disclose the whole bag of tricks and be used to make coloured non-silicone hydrogel contact lens (for example referring to being disclosed in the U.S. patent No. 4,668,240,4,857,072,5,272,010 and 5,414,477 and the method for U.S. patent application publication number 2003/0054109 and 2004/0044099).Commercial Tinted contact lenses is by for example hydroxyethyl methacrylate (HEMA) based aquagel (being the copolymer of HEMA and other comonomer and/or the crosslinking agent) preparation of non-silicone hydrogel material.Those non-silicone hydrogel lens generally do not have high oxygen permeability.Well-known contact lenses must allow that the oxygen (that is: oxygen) from surrounding air arrives cornea, because cornea can not be organized the oxygen that receives from blood supply as other.If there is not enough oxygen to reach cornea, cornea will expand.Long term hypoxia causes undesirable blood vessel hyperplasia in the cornea.Hydrogel contact lens closely meets shape of eyes, so oxygen is not easy to walk around these lens.Therefore, hydrogel contact lens must allow that oxygen diffuses through lens and arrives cornea, promptly from the outer surface to the inner surface, have high relatively oxygen permeability (promptly crossing the oxygen permeability of lens thickness) and arrive cornea, and corneal health has minimum side effect so that allow enough oxygen infiltration scioptics.

In recent years, silicone hydrogel contact lenses, for example Focus NIGHT﹠DAY ^TM(CIBAVISION), becoming becomes more and more popular, because high oxygen permeability and comfortableness that they provide are of value to corneal health.Yet almost development is not used to make colored silicone hydrogel contact lenses, the method for the colored silicone hydrogel contact lenses of especially special (MTO) or customization.Typically the colored silicone hydrogel contact lenses of MTO that makes by direct cutting or customization can with write out a prescription coupling and/or have the basic arc (base curve) that the patient wants of patient.

Therefore, need a kind of method of making the colored silicone hydrogel contact lenses of MTO or customization.

Summary of the invention

On the one hand, the invention provides the method for making colored silicone hydrogel contact lenses, this method comprises: the mould that is provided for valve calotte (bonnet) casting molding, wherein this mould comprises the forming surface (molding surface) with optical quality, and wherein this forming surface limits one of them of silicone hydrogel contact lenses rear surface and front surface; On printing ink at least a portion with color coat paint mould molding face, wherein this printing ink comprises at least a colouring agent and the polymer adhesive that contains siloxanes; Solidify this color coat and form coloured film, this film contacts with forming surface but is not attached on this forming surface with covalent manner; Form fluent material with the lens that comprise at least a vinyl monomer that contains siloxanes or big monomer and at least a hydrophilic ethylene monomer and fill this mould; Make lens-forming material soak one sufficiently long period of this coloured film, make a part of lens-forming material penetrate into the space between coloured film and the forming surface, simultaneously partially or completely by separating this coloured film on the forming surface; Solidify this lens-forming material in mould, form the valve calotte of forming surface that has corresponding to one of them of contact lenses front surface and rear surface, wherein this valve calotte comprises and being fixed in wherein and/or the coloured film on it; Remove this valve calotte by mould; With solidify behind this valve calotte and/or the dry sufficiently long time to improve this valve calotte machinability at room temperature; And form front surface or rear surface by on the side relative, directly cutting this valve calotte, obtain colored silicone hydrogel contact lenses thus with forming surface.

On the other hand, the invention provides the method for making colored silicone hydrogel contact lenses, this method comprises: the mould that is provided for valve calotte casting molding, wherein this mould comprises the forming surface with optical quality, and wherein this forming surface limits one of them of silicone hydrogel contact lenses rear surface and front surface; On printing ink at least a portion with color coat paint mould molding face, wherein printing ink comprises at least a colouring agent and polymer adhesive, and wherein binder polymer comprises the segment that derives from least a hydrophilic ethylene monomer or big monomer; Randomly solidify color coat and be attached to coloured film on the forming surface to form not with covalent manner; Form fluent material with the lens that comprise at least a vinyl monomer that contains siloxanes or big monomer and at least a hydrophilic ethylene monomer and fill this mould; In mould, solidify this lens-forming material, formation has the valve calotte corresponding to the forming surface of one of them of contact lenses front surface and rear surface, wherein this valve calotte comprises and being fixed in wherein and/or color coat on it or film, and wherein the forming surface of this valve calotte comprises at least a portion of color coat or film; Remove this valve calotte by mould; With solidify behind this valve calotte and/or dry sufficiently long a period of time to improve this valve calotte machinability at room temperature; And form front surface or rear surface by on the side relative, directly cutting this valve calotte, obtain colored silicone hydrogel contact lenses thus with forming surface.

The specific embodiment

Now will be in detail with reference to embodiment of the present invention.It will be apparent for a person skilled in the art that do not depart from the scope of the present invention or the situation of spirit under, can carry out various changes and variation in the present invention.For example, the feature of describing or illustrating as the part of an embodiment can be used for another embodiment to produce other embodiments.Therefore, the present invention be intended to cover with claims with and the scope of coordinate in same this type of change and variation.Other purpose of the present invention, feature and aspect are disclosed or apparent by it by following detailed description.What it will be understood by those skilled in the art that is that this discussion only is the exemplary description of embodiment, is not to be intended to limit the wideer aspect of the present invention.

Unless otherwise defined, otherwise whole technology used herein has the meaning identical with those skilled in the art in the invention's general understanding with scientific terminology.In general, nomenclature used herein and experimental arrangement are known and commonly used in this area.For example the conventional method that provided of prior art and various general reference book can be used for these programs.If term provides with odd number, the inventor is also intended to use the plural number of term.Nomenclature used herein and experimental arrangement as described below are known and commonly used in the art.

" contact lenses " refer to be placed on wearer's eyes or inner structure.User's eyesight can be corrected, improves or be changed to contact lenses, except there is no need it is this situation.Contact lenses can be any known suitable materials of any prior art or later exploitation, can be SCL, hard lens or hybrid lens.Typically, contact lenses have the circumferential edges that front surface and relative rear surface and front surface and rear surface diminish therein gradually.

" front or the front surface " of contact lenses used herein refers in the process of wearing the lens surface away from eyes.Typically be antecurvature (frontcurve) that the front surface of convex surface also can be described as lens basically.

Contact lenses used herein " back side or rear surface " refer in the process of wearing the lens surface towards eyes.Typically be the basic arc that the back side of concave surface also can be described as lens basically.

" Tinted contact lenses " refers to be printed with on it contact lenses (hard or soft) of coloured image.

" coloured image " is to describe motif (iris shape pattern for example, Wild Eye ^TMPattern, special (MTO) pattern etc.), the counter-rotating sign allows that the user easily operates and insert contact lenses, and/or the contact lenses goods is preserved unit (SKU) or digital printed form or bar code form.Coloured image can be monochrome image or multicolor image.Coloured image is digital picture preferably, but it can also be an analog image.

" color coat " refers to the coating on the object and wherein has the coloured image of printing.

" colouring agent " is meant dyestuff or pigment or its mixture that is used for printing color image on goods.

" dyestuff " is meant the material that dissolves in solvent and be used for giving color.Dyestuff is translucent typically, absorbs and scattered light not.Dyestuff can cover the non-optical zone of the optical region and the contact lenses of contact lenses.Almost any dyestuff all can be used for the present invention, as long as it can be used for device as described below.These dyestuffs comprise fluorescent dye, phosphorescent coloring and conventional dyestuff.

" fluorescence " be meant by a wavelength absorption visible light or ultra-violet radiation subsequently almost immediately with longer wavelength emission cause luminous.When the ultra-violet radiation of light or incident stopped, fluorescent emission almost stopped immediately.

" phosphorescence " is by postponing to launch cause luminous with different wavelength subsequently a wavelength absorption radiation.After incident radiation stopped, phosphorescent emissions continued to prolong a period of time.

" pigment " is meant and is suspended in flour insoluble in the liquid.Pigment is used for giving color.In general, to compare dyestuff opaquer for pigment.

Here the term of Shi Yonging " conventional or non-pearlescent pigment " is to be used to describe anyly give the absorption pigment of color based on diffuse scattering optics principle, and its color and its geometry have nothing to do.Simultaneously can use any suitable non-pearlescent pigment, preferred non-pearlescent pigment is insoluble in heat-resisting, nontoxic and the aqueous solution at present.The example of preferred non-pearlescent pigment comprises any colouring agent that is used for medical apparatus and is ratified by FDA of allowing, as D﹠amp; C Blue No.6, D﹠amp; C Green No.6, D﹠amp; C VioletNo.2, carbazole violet, some copper complex, some chromated oxide, various ferriferous oxide, phthalocyanine (PCN) are green, phthalocyanine (PCN) indigo plant, titanium dioxide etc.Can be used for the present invention referring to the cited a series of colouring agents of Marmiom DM Handbook of U.S.Colorants (U.S colouring agent Marmiom DM handbook).The preferred embodiment of non-pearlescent pigment comprises (C.I. be chromaticity index number), but be not limited to, blue, phthalocyanine blue (pigment blue 15: 3 C.I.74160), cobalt blue (pigment blueness 36, C.I.77343), the blue B2G (Clariant) of toner blue or green BG (Clariant), Permajet; Green, and phthalocyanine green (pigment Green 7, C.I.74260) and chrome green; Yellow, red, brown and black, various ferriferous oxides; PR122, PY154; Purple, carbazole violet; Black, Monolith are deceived C-K (CIBA SpecialtyChemicals).

" pearly-lustre " is meant to have pearly luster; Similar pearl on physical appearance; Or have almost uncertain slight bluish in grey.

" pearlescent pigment " refers to the classification of interference (effect) pigment, it is with high refractive index material (metal oxide for example, for example titanium dioxide or iron oxide) optically thin coating coating low refractive index material transparent sheet (for example, transparent mica sheet), and the optical principle disturbed of main based thin film give its color.The optically thin coating of metal oxide can comprise individual layer or multiple thin layer of metal oxide.Optically thin coating on this sheet of paint is facilitated interference effect, and it allows that outward appearance changes according to the illumination and the condition of watching.Color is by coating layer thickness, refractive index and light angle decision.Because part sees through the mica sheet transmission from mica sheet reflection and part, so optically thin coating also is to cause the reason of press polish effect.Such pigment can provide pearly luster and rainbow effect.

Mica sheet pearlescent pigment with oxide coating can be by Iselin, N.J. Englehard Corp. is commercial obtaining under " Mearlin Pigment " production line, for example " Hi-Lite InterferenceColors ", " Dynacolor Pearlescent Pigments ", " MagnaPearl ", " Flamenco, " and " Celini Colors ".The other manufacturer of pearlescent colorants is: Savannah, and the Kemira of Georgia, Inc., the commodity of this pigment are called " Flonac Lustre Colors "; And Hawthorne, the EM Industries of N.Y., Inc., the commodity of this pigment are called " Affair Lustre Pigments ".

" hydrogel " is meant can absorb the polymeric material of 10wt% water at least when abundant hydration.In general, hydrogel material obtains by at least a hydrophilic monomer polymerization or combined polymerization under the condition that has or do not exist other monomer and/or big monomer.

" siloxanes aquogel " is meant by containing at least a vinyl monomer of siloxanes or the hydrogel that at least a polymerisable compound combined polymerization that contains the big monomer of siloxanes obtains of containing.

What " hydrophily " used herein described is to compare the easier material that combines with water or its part with lipid.

" lens-forming material " be meant can heat cure or photochemical curing (being polymerization and/or crosslinked) obtain the polymerisable compound (or preparaton) of cross-linked polymer.The curing or " the photochemical ground " of polymerization about polymerisable compound or material or lens-forming material used herein is meant that this curing (for example crosslinked and/or polymerization) carries out for example ultra-violet radiation, ionising radiation (for example gamma-rays or X-radiation), microwave radiation etc. by actinic radiation.Heat cure or photochemical curing are well known to a person skilled in the art.Lens-forming material is well known to a person skilled in the art.

" prepolymer " is meant can photochemical curing or heat cure or chemosetting (for example crosslinked and/or polymerization) and obtain the starting polymer of polymer crosslinked and/or polymerization, and the molecular weight of resulting polymers is far above starting polymer." crosslinkable prepolymer " be meant when actinic radiation can crosslinked acquisition cross-linked polymer starting polymer, the molecular weight of gained cross-linked polymer is far above starting polymer.

" monomer " be meant can polymerization low molecular weight compound.Low-molecular-weight typically refers to mean molecule quantity and is lower than 700 dalton.

" vinyl monomer " used herein refers to has ethylenically unsaturated group and can photochemical polymerization or the low molecular weight compound of thermal polymerization.Low-molecular-weight typically refers to mean molecule quantity and is lower than 700 dalton.

Term " alkene class unsaturated group " or " ethylenically unsaturated group " here use with broad sense, the meaning be comprise contain at least one＞any group of C=C＜group.Exemplary ethylenically unsaturated group includes, but not limited to acryloyl group, methacryl, pi-allyl, vinyl, styryl or other contains the group of C=C.

" hydrophilic ethylene monomer " used herein is meant can form when abundant hydration and can absorbs the vinyl monomer of the homopolymers of 10wt% water at least.

" hydrophobicity vinyl monomer " used herein is meant when abundant hydration can form the vinyl monomer that can absorb the homopolymers that is lower than 10wt% water.

" big monomer " refers to the compound or the polymer of the medium or HMW that contains the functional group that can carry out further polymerized/cross-linked reaction.Medium and HMW is meant that generally mean molecule quantity is greater than 700 dalton.Preferred big monomer contains ethylenically unsaturated group also can photochemical polymerization or thermal polymerization.

" molecular weight " of polymeric material used herein (comprise monomer material or big monomer material) is meant number-average molecular weight, unless specify in addition or experimental condition indicates in addition.

" polymer " is meant that material passes through the material that one or more monomers of polymerized/cross-linked, big monomer and/or oligomer form.

" binder polymer " refers to crosslinkable polymer, it can pass through crosslinking agent or crosslinked with chemistry or physics mode (for example humidity, heat, ultraviolet radiation etc.) through raying, with capture colouring agent it is adhered on the medical apparatus (preferred contact lenses) or within, this is a term known in the art.

" light trigger " refers to by utilizing the chemicals of light-initiated radical crosslinking and/or polymerisation.The light trigger that is fit to includes, but not limited to benzoin methyl ether, diethoxy acetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenylketone, Darocure ^Type and Irgacure ^Type, preferred Darocure ^1173 and Irgacure ^2959.Azo-type initator [for example 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile)] can be used as light trigger or thermal initiator.

" thermal initiator " refers to by utilizing heat energy to cause the chemicals of radical crosslinking and/or polymerisation.The example of the thermal initiator that is fit to includes, but not limited to 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile), peroxide such as benzoyl peroxide etc.Preferred thermal initiator is azodiisobutyronitrile (AIBN).

Term used herein " fluid " refers to the material that can flow as liquid.

" interpenetrating polymer networks (IPN) " used herein broadly refers to the tight network of two or more polymer, and wherein at least a polymer is synthetic and/or crosslinked in the presence of another kind.The technology of preparation IPN is well known to a person skilled in the art.General program is referring to the U.S. patent No. 4,536,554,4,983,702,5,087,392 and 5,656,210.Polymerization is generally carried out in the temperature range of about room temperature to 145 ℃.

" the oxygen permeability " of lens used herein is the speed that Oxygen Flow is crossed specific ophthalmic lens.Oxygen permeability Dk/t uses the unit representation of barrers/mm usually, and wherein t is the material average thickness [mm of unit] on the whole measurement area, and " barrer/mm " is defined as:

[(cm ³Oxygen)/(cm ²) (second) (mm ²Hg)] * 10 ^-9

Intrinsic " oxygen permeability " Dk of lens material does not rely on lens thickness.Intrinsic oxygen permeability is the speed that oxygen passes material.Oxygen permeability is unit representation with barrers usually, and wherein " barrer " is defined as:

[(cm ³Oxygen) (mm)/(cm ²) (second) (mm ²Hg)] * 10 ^-10

These are this area units commonly used.Therefore, for consistent with the use of this area, unit " barrer " has the implication that is defined as above.For example, Dk is that 90 barrer (" oxygen permeability barrer ") and thickness are that the Dk/t that the lens of 90 microns (0.090mm) have is 100 barrer/mm (oxygen permeability barrer/mm).

" ion permeability " of scioptics is relevant with the lonoflux diffusion coefficient.This lonoflux diffusion coefficient D, Fick's law (Fick ' s law) is following to be determined by using:

D＝-n’/(A×dc/dx)

N '=ion-transfer speed [mol/ branch] wherein

A=lens exposure area [mm ²]

D=lonoflux diffusion coefficient [mm ²/ minute]

Dc=concentration difference [mol/L]

Dx=lens thickness [mm]

The lonoflux diffusion coefficient D is preferably greater than about 1.5 * 10 ^-6Mm ²/ minute, yet more preferably greater than about 2.6 * 10 ^-6Mm ²/ minute and most preferably greater than about 6.4 * 10 ^-6Mm ²/ minute.

" room temperature " (or " environment temperature ") is defined as 22 ± 3 ℃.

" machinability " of term material refers to uses typical this material of lens cutting apparatus can be machined into the contact lenses with optical quality.A standard of material machinability is its glass transition temperature (T _g).T _gThe single-phase polymeric material that is lower than room temperature is considered to cut under the room temperature too soft, however T _gBe higher than those of room temperature, preferably be higher than room temperature 3 degree at least, have enough room temperature cutting hardness.Microcosmic heterogeneous polymerization material can show an apparent single T _gAn or more than T _gAs long as the material of the phase of preponderating in the microcosmic heterogeneous polymerization material has the T that is higher than room temperature _g, it just can at room temperature cut into contact lenses.Here " phase of preponderating " is defined as the phase of decision whole material (body or operation) hardness in the heterogeneous material.

Term " valve calotte " or " lens blank that single face is molded " refer to the polymer button (button) that obtains by casting molding or rotated mold filing lens-forming material in mould, and wherein at least one in two opposite faces of this valve calotte has corresponding to one of them optics finished surface of contact lenses front surface and rear surface.Term refers to the surface of contact lenses or the zone on the contact lens surface about the surface or " the optics processing " in lip-deep zone, wherein should the surface or the zone do not need to carry out other processing, for example polishing or cut.People can also be by intending valve calotte processing lens.Intend the valve calotte and be meant that the material two sides all needs to cut so that obtain the parts of contact lenses.This base part will allow the positive and negative surface design of lens to have flexibility, and spillage of material is minimized.

The present invention relates to make colored silicone hydrogel contact lenses, especially the method for the colored silicone hydrogel contact lenses of MTO or customization.Method of the present invention may further comprise the steps: be provided for the mould of molding valve calotte, wherein mould comprises the forming surface with optical quality, and wherein this forming surface limits one of them of silicone hydrogel contact lenses rear surface and front surface; On printing ink at least a portion with color coat paint mould molding face, wherein this printing ink comprises at least a colouring agent and the polymer adhesive that contains siloxanes; Solidify this color coat and form coloured film, this film contacts with forming surface but is not attached on this forming surface with covalent manner; Form fluent material with the lens that comprise at least a vinyl monomer that contains siloxanes or big monomer and at least a hydrophilic ethylene monomer and fill this mould; Make lens-forming material soak one sufficiently long period of this coloured film, make a part of lens-forming material penetrate into the space between coloured film and the forming surface, simultaneously partially or completely by separating coloured film on this forming surface; Cured lens forms material in mould, forms the valve calotte of forming surface that has corresponding to one of them of contact lenses front surface and rear surface, and wherein this valve calotte comprises and being fixed in wherein and/or the coloured film on it; Remove this valve calotte by mould; With solidify behind this valve calotte and/or the dry one sufficiently long period to improve valve calotte machinability at room temperature; And, obtain colored silicone hydrogel contact lenses thus by on the side relative, directly cutting this valve calotte formation front surface or rear surface with forming surface.Solidify the back and/or dry valve calotte can carry out when the valve calotte is in mould or after removing mould.

According to the present invention, printing ink typically comprises colouring agent, contains the binder polymer of siloxanes and optional adhesion promotor.

Solvent can be the mixture of water, organic or inorganic solvent, several organic solvents, or water and one or more mixtures water-soluble or the water miscibility organic solvent.Can use any known suitable solvent, need only the stability that they can dissolve the adhesive in the printing ink of the present invention and help colouring agent.Exemplary solvent comprises, but be not limited to, water, acetone, alcohol (methyl alcohol for example, ethanol, propyl alcohol, isopropyl alcohol, cellosolvo etc.), ethylene glycol, ketone, ester, cyclopentanone, cyclohexanone, oxolane, acetone, N-methyl-2-2-pyrrolidone N-, dimethyl formamide, acetophenone, carrene, methyl-sulfoxide, gamma-butyrolacton, ethylene dichloride, isophorone, o-dichlorohenzene, oxolane, diacetone alcohol, methyl ethyl ketone, acetone, the 2-nitropropane, ethylene glycol monoethyl ether, propylene carbonate, cyclohexanol, chloroform, trichloro-ethylene, 1,4-two  alkane, ethyl acetate, ethyl lactate, ethylene glycol monobutyl ether (EGMBE), chlorobenzene, nitroethane, glycol monoethyl ether, butyl acetate, the 1-butanols, methyl iso-butyl ketone (MIBK), nitromethane, toluene, ethanol, diethylene glycol (DEG), benzene, diethyl ether, monoethanolamine, carbon tetrachloride, propane diols, hexane, ethylene glycol and formamide.

Colouring agent can be a dyestuff, or preferred pigments.In general, dyestuff can not provide the available height of pigment opaque printing.Preferably, the colouring agent in the printing ink of the present invention comprises at least a pigment.Colouring agent also can be the mixture of two or more pigment, and they are in conjunction with providing the color of wanting, because any color all can be by only obtaining two or more former mixture of colours." primary colors " is meant cyan, yellow, peony, white and black as defined herein.Colouring agent also can be the mixture of at least a pigment and at least a dyestuff.Those skilled in the art will know that and how to select colouring agent.

Non-pearlescent pigment preferred size is about 5 microns or littler.Bigger granules of pigments can grind to form than granule.Many methods well known in the art can be used for ground pigment.The exemplary preferred method that reduces the pigment granularity comprises high speed agitator, Kady grinder (rotor stator dispersal device), colloid mill, homogenizer, microfluidization device, sonar device (sonalator), ultrasonic grinding machine, roll mill, ball mill, roller mill, oscillatory type ball mill, grater, sand mill, variable power decentralized device, three-roll grinder, Banbury (Banbury) mixer or well known to a person skilled in the art other method.Under the situation of pearlescent pigment, importantly make the destruction of sheet minimize and keep enough dispersion level in the process.Pearlescent pigment needs gently to handle in the mixed process, and they can not be ground or stand long-time mixing, grinding or high shear, because this generic operation can damage pigment.Size distribution, shape and orientation influence final outward appearance consumingly.Should avoid grinding, high shear mixing or long-time processing, because this generic operation may cause coating of metal oxides to be peeled off, sheet is cracked, sheet agglomeration and sheet extruding to pearlescent pigment.The peeling off of metal oxide, extruding, cracked and agglomeration will reduce pearlescent effect.

According to the present invention, the binder polymer that contains siloxanes should comprise crosslinkable groups, and this group is selected from that (wherein R is hydrogen or C by ethylenically unsaturated group, hydroxyl-OH, amino-NHR ₁-C ₈Alkyl), carboxylic acid-COOH, epoxy, acid amides-CONHR, isocyanates, peroxide, perester, acid anhydrides, alkoxy silane, silanol, acetoxylsilane, silane, halosilanes and their group in conjunction with composition.Printing ink can contain or not contain adhesion promotor, depends primarily on the kind of the crosslinkable groups of the binder polymer that contains siloxanes that will use.

The binder polymer that wherein contains siloxanes in the printing ink comprises ethylenically unsaturated group as crosslinkable groups, can heat cure or the photochemical coloured film that solidify to form with the color coat of ink printing on the mould molding face.Do not need adhesion promotor.This type of example that contains the binder polymer of siloxanes is the olefinic functional derivative with silicon-containing polymer of side chain functionalities.What term used herein " olefinic is functionalized " will be described is that ethylenically unsaturated group is incorporated in the polymer that contains siloxanes.Carry out the preferably combined polymerization product of polymerisable compound of the functionalized siloxane-containing copolymer of olefinic, it comprises (a) at least a hydrophilic ethylene monomer, (b) at least a functionalized vinyl monomer that contains at least one side chain functionalities, this side chain functionalities is preferably selected from by hydroxyl (OH), primary amino radical (NH ₂), secondary amino group (NHR), carboxyl (COOH), epoxy radicals, aldehyde radical (CHO), amide groups (CONH ₂), acid halide group (COX, X=Cl, Br or I), isothiocyanate group, NCO, halide group (X, X=Cl, Br or I), anhydride group and they in conjunction with group of forming and (c) at least a vinyl monomer or the big monomer that contains siloxanes.Polymerisable composition can also comprise polymerization initiator (being light trigger or thermal initiator), is preferred for the solvent and the chain-transferring agent of printing ink.The olefinic of siloxane-containing copolymer is functionalized to be to be undertaken by silicon-containing polymer and olefinic functionalized reagent reaction, the olefinic functionalized reagent comprises ethylenically unsaturated group and can form the group of covalent bond with the functional group reactions of siloxane-containing copolymer, and this is known in those skilled in the art.Preferred olefinic functionalized reagent's example comprises, but be not limited to GMA, glycidyl acrylate, methacrylic acid 2-isocyanato ethyl (IEM), N-hydroxymethyl acrylamide (NHMA), acryloyl chloride, methacrylic chloride, methacrylic acid, acrylic acid, methacrylic acid 2-bromo ethyl ester and methacrylic anhydride.

Wherein the siloxanes binder polymer that contains in the printing ink comprises alkoxysilane group, silanol group, acetoxylsilane base, silylation or halosilanes group as crosslinkable groups, can solidify by humidification activation with the color coat of ink printing on the mould molding face.When being exposed to moisture following time, alkoxy silane, acetoxylsilane, silane or halosilanes form silanol.Silanol reacts the formation siloxane bond each other.Therefore, containing the polymer chain of silanol side group (or precursor) can be crosslinked in conjunction with forming by forming siloxane bond.If humidification activation, crosslinked will in the polymer hydration process, formation.Preferred potential crosslinkable side group is halosilanes and alkoxy silane, and alkoxy silane is most preferred.Comprising alkoxy silane, silanol, acetoxylsilane, silane or halosilanes group is those of U.S. Patent application publication No.2003/0054109 that are disclosed in common transfer as the example of the binder polymer that contains siloxanes of crosslinkable groups.This type of binder polymer that contains siloxanes comprises (A) by combined polymerization and polymerizable mixture (B) obtains: (A) have the vinyl monomer of potential crosslinkable groups, this crosslinkable groups is selected from the group of being made up of alkoxy silane, silanol, acetoxylsilane, silane or halosilanes group; (B) do not contain can with the vinyl monomer of the group of the potential crosslinkable groups coreaction of monomer (A).

For example, contain polymerisable halosilanes or alkoxysilane compound containing trialkylsilyl group in molecular structure and do not have the polymerizable mixture of the vinyl monomer of active hydrogen atom can hot copolymerization or photochemical copolymerization, form and have alkoxy silane or halosilanes group the binder polymer that contains siloxanes as crosslinkable groups.

The example of polymerisable alkoxysilane compound containing trialkylsilyl group in molecular structure comprises, but be not limited to: the methacryloxyethyl trimethoxy silane, the methacryloxyethyl methyl dimethoxysilane, methacryloxyethyl dimethyl methyl TMOS, the methacryloxyethyl triethoxysilane, the methacryloxyethyl methyldiethoxysilane, the methacryloxyethyl dimethylethoxysilane, methacryloxy-propyl trimethoxy silicane, the methacryloxypropyl methyl dimethoxysilane, methacryloxypropyl dimethyl methyl TMOS, the methacryloxypropyl triethoxysilane, the methacryloxypropyl methyldiethoxysilane, the methacryloxypropyl dimethylethoxysilane, styryl ethyl trimethoxy silane, and 3-(N-styryl methyl-2-aminoethylamino) propyl trimethoxy silicane hydrochloride.These compounds can use separately or use with two or more the mixture in them.

The example of polymerisable halo silane compound includes, but are not limited to: methacryloxypropyl dimethyl dichlorosilane (DMCS), methacryloxypropyl trichlorosilane, 3-methacryloxypropyl dimethylchlorosilane and methacryloxyethyl trichlorosilane.

Do not have the example of the vinyl monomer of active hydrogen atom to comprise: the N-vinyl heterocyclic monomers, as N-vinyl-2-Pyrrolidone (NVP); C ₁-C ₆Alkyl vinyl ether is as vinyl ethyl ether; The C of acrylic or methacrylic acid ₁-C ₆Arrcostab is as methyl methacrylate and propyl acrylate; C ₁-C ₆Ring-alkylated styrenes is as t-butyl styrene; Vinyl monomer is as vinyl chloride and vinyl acetate; Diene monomer is as isoprene; N, N-dialkyl group (methyl) acrylamide or acrylamide (for example N,N-DMAA (DMA)); C with acrylic or methacrylic acid ₁-C ₆Alkoxy C ₁-C ₆Arrcostab is as methacrylic acid ethoxy ethyl ester (EOEMA) or acrylic acid methoxyl group propyl ester.These monomers can use separately or use with two or more the mixture in them.

The binder polymer that wherein contains siloxanes in the printing ink comprises crosslinkable groups, and this group is selected from that (wherein R is hydrogen or C by hydroxyl-OH, amino-NHR ₁-C ₈Alkyl), carboxyl-COOH, epoxy radicals, amide groups-CONHR and they in conjunction with the group of forming, comprise adhesion promotor in the preferred printing ink.An example that contains the binder polymer of siloxanes can be the copolymerization product that comprises the polymerizable mixture of following material: (i) at least a hydrophilic ethylene monomer; The (ii) at least a functionalized vinyl monomer that contains at least one functional group that is selected from the group of being made up of following group: (wherein R is hydrogen or C for hydroxyl-OH, amino-NHR ₁-C ₈Alkyl), carboxyl-COOH, epoxy radicals, amide groups-CONHR and their combination; (iii) at least a monomer or the big monomer that contains siloxanes ethene.Also comprise one or more and be selected from component by the group of polymerization initiator (being light trigger or thermal initiator), chain-transferring agent and solvent composition.Polymerizable mixture can also comprise polymerization initiator (being light trigger or thermal initiator), is preferred for the solvent and the chain-transferring agent of printing ink.Polymerizable mixture can be chosen wantonly and comprise the hydrophobicity vinyl monomer, for example methacrylic acid 2-ethoxy ethyl ester (EOEMA).

The example that contains the vinyl monomer of siloxanes comprises, but be not limited to the methacryloxy alkylsiloxane, 3-methacryloxypropyl pentamethyl disiloxane, two (methacryloxypropyl) tetramethyl disiloxane, the dimethyl silicone polymer of monomethacrylatesization, the dimethyl silicone polymer of sulfydryl end-blocking, N-[three (trimethylsiloxy) silicyl propyl group] acrylamide, N-[three (trimethylsiloxy) silicyl propyl group] Methacrylamide, three (pentamethyl dimethylamino silane oxygen base (siloxyanyl))-3-metering system acid groups close propyl silane (T2) and three (trimethyl silyloxy silicyl propyl group) methacrylate (TRIS).Preferably containing siloxanyl monomers is TRIS, and it is meant 3-methacryloxypropyl three (trimethylsiloxy) silane, is expressed as CASNo.17096-07-0.Term " TRIS " also comprises the dimer of 3-methacryloxypropyl three (trimethylsiloxy) silane.

Can use any known suitable big monomer that contains siloxanes.The particularly preferred big monomer that contains siloxanes is selected from US 5,760, the group of describing in 100 of being made up of big monomer A, big monomers B, big monomer C and big monomer D.

Almost any hydrophilic ethylene monomer all can be used for the present invention.The hydrophilic monomer that is fit to is the low alkyl group (C that the hydroxyl of (this is not exhaustive inventory) acrylic acid and methacrylic acid replaces ₁-C ₈) ester, acrylamide, Methacrylamide, (rudimentary pi-allyl) acrylamide and Methacrylamide, the acrylate of ethoxylation and methacrylate, (low alkyl group) acrylamide and Methacrylamide that hydroxyl replaces, the low alkyl group vinyl ethers that hydroxyl replaces, sodium vinyl sulfonate, the styryl sodium sulfonate, 2-acrylamido-2-methyl propane sulfonic acid, the N-vinyl pyrrole, N-vinyl-2-Pyrrolidone, 2-vinyl  azoles quinoline, 2-vinyl-4,4 '-dialkyl group  azoles quinoline-5-ketone, 2-and 4-vinylpridine, has alkene class (vinylically) unsaturated carboxylic acid of 3-5 carbon atom altogether, hydrogen base (low alkyl group) (wherein term " amino " also comprises quaternary ammonium), the list of acrylic acid and methacrylic acid (low-grade alkyl amino) (low alkyl group) ester and two (low-grade alkyl amino) (low alkyl group) ester, allyl alcohol etc.Wherein preferred hydrophilic ethylene monomer is N, N-DMAA (DMA), methacrylic acid 2-hydroxyl ethyl ester (HEMA), hydroxy-ethyl acrylate (HEA), hydroxypropyl acrylate, hydroxy propyl methacrylate (HPMA), methacrylic acid 2-hydroxy propyl ester trimethyl ammonium hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glyceral methacrylate (GMA), N-vinyl-2-Pyrrolidone (NVP), the dimethyl aminoethyl Methacrylamide, acrylamide, Methacrylamide, allyl alcohol, vinylpyridine, N-(1,1-dimethyl-3-oxo butyl) acrylamide, acrylic acid and methacrylic acid.

Among the present invention, as functionalized vinyl monomer, can use any known suitable vinyl monomer that contains at least one functional group that is selected from the group of being made up of following group: hydroxyl-OH, (wherein R is hydrogen or C to amino-NHR ₁-C ₈Alkyl), carboxyl-COOH, epoxy radicals, amide groups-CONHR, and their combination.This type of vinyl monomer preferred examples comprises methacrylic acid (MAA), acrylic acid, GMA, glycidyl acrylate, HEMA, HEA and N hydroxymethyl acrylamide (NHMA).

Should be understood that in the polymerisable compound that vinyl monomer not only can be used as the hydrophilic ethylene monomer but also can be used as functionalized vinyl monomer is used to prepare the polymer that contains siloxanes with side chain functionalities.The vinyl monomer of preferred hydrophilic does not have functional group (for example DMA, NVP).

Any known suitable chain-transferring agent can be used for the present invention.The example of preferred chain-transferring agent comprises the dimethyl silicone polymer of ethane thiol, mercaptoethanol, dithioglycol, dimercaptopropane and sulfydryl end-blocking.

According to the present invention, the copolymerization that is used for preparing binder polymer can cause by heating or actinic radiation (for example UV) in polymerizable mixture, this polymerizable mixture comprises solvent (as ethanol or cyclopentanone), thermal initiator (for example AIBN) or light trigger, chain-transferring agent (as ethyl mercaptan (EtSH)), the hydrophilic ethylene monomer of no functional group (for example DMA), functionalized vinyl monomer (for example HEMA, MAA or GMA) with at least one functional group, the dimethyl silicone polymer of alkoxy silane monomer (for example TRIS) and monomethacrylatesization.Possible preferred polymeric reaction is not exclusively produced the binder polymer that is dissolved in solvent thus, and it preferably contains the vinyl monomer of some remained unreacted.The polyblend that only contains adhesive and unconverted monomer also is desirable, because solvent can be eliminated.Unconverted monomer can be used for helping control printing ink rheological property, and changes into polymer in the process of ink solidification and/or the curing of valve calotte.The polymerization level of how controlling as well known to those skilled in the art.

The binder polymer that contains siloxanes can also be polyurethane and/or the polyurea polymer with at least two kinds of functional groups, and this functional group can be hydroxyl, amino (uncle or secondary), isocyano group.The polyurethane/polyurea binder polymer that contains siloxanes can prepare by following mixture reaction (polymerization), this mixture contains: (a) at least a α, the polysiloxanes that alpha, omega-dihydroxy is alkyl-blocked, (b) optional at least a amino-or poly-(alkylene oxide) (for example poly-(oxyalkylene) diamines or PAG) of hydroxyl-end-blocking, (c) optional at least a compound with at least two hydroxyls or amino (uncle or secondary), (d) at least a vulcabond and (e) optional polyisocyanates.

The polysiloxanes of dihydroxy end-blocking can be synthetic according to any known method, and is for example, synthetic by the reaction of disiloxane or dimethoxy dimethylsilane or di ethoxy di methyl-monosilane and cyclomethicone is come.The example of aminoalkyl PAG is so-called J effamines ^Compound.Exemplary poly-(aklylene glycol) comprises, but be not limited to poly-(ethylene glycol), poly-(propane diols), poly-(ethylene glycol)/poly-(propane diols) block polymer, poly-(ethylene glycol)/poly-(propane diols)/poly-(butanediol) block polymer, PolyTHF, poloxamer (poloxamer) and their mixture.

" adhesion promotor " refers to comprise the compound (or crosslinking agent) of two or more functional groups.Cross-linker molecules can be used for crosslinked two or more monomers or polymer molecule.Many different cross-linking reactions are used in and produce chemical bonding between the different binder polymer molecules to capture painted particle.Most crosslinking agent be by two or polyfunctional reaction active groups differentiate.For example, can use two phenolic compounds, diepoxides, two melamines, vulcabond or two urea formaldehydes.Polyfunctional phenoplasts have following structure: (HOH ₂CPh) _n-R ₉, wherein Ph is a phenolic groups.The multi-functional epoxyization thing has following structure: (CH ₂OCH) _n-R ₉Polyfunctional aldehyde has following structure: (HCO) _n-R ₉Or (CH ₃CO) _n-R ₉Polyfunctional isocyanates has following structure: (OCN) _n-R ₉Melamine resin has following structure: (HOH ₂C-Mel) _n-R ₉, wherein melamine is

In the above example, R ₉Can be aliphatic, alicyclic, aliphatic-alicyclic, aromatics, aliphatic-aromatic hydrocarbon, vinyl alcohol, polyvinyl butyral or vinyl acetate, and n be the number greater than 1.Can use functional group's (epoxides that promptly has isocyanates) of mixing.

Exemplary isocyanate compound comprises hexamethylene diisocyanate (HMDI), 2,4-toluene di-isocyanate(TDI) and two (isocyanato-phenyl) methane.The group of exemplary ring-containing oxide comprises bisphenol-A propoxylate (1PO/ phenol) diglycidyl ether, diepoxides and chloropropylene oxide.

According to the present invention, printing ink can also comprise one or more components that is selected from the group of being made up of thermal initiator, light trigger, diluent, surfactant, wetting agent, antimicrobial, antioxidant, anti-agglomerating agent and other additive well known in the art.

According to the present invention, diluent can be the solution of solvent or one or more vinyl monomers.

Be used for printing ink of the present invention and should have the adhesiveness good silicone hydrogel contact lenses." to contact lenses or the good adhesiveness of siloxanes (silicon) hydrogel contact lens " about color coat or ink device used herein refers to the color coat (having coloured image) that produces with printing ink on lens at least can be by the finger friction test, preferably by finger friction test and the sonicated survival test in methyl alcohol (or other solvent that is fit to, for example isopropyl alcohol).

The finger friction test is by by the contact lenses that shift out hydration in the packaging solution (for example salt solution), and rubs about at the most 10 seconds at counting between two fingers or between finger and the palm.The observed result of colouring agent bleeding, stain or the visible and microcosmic (～10 *) peeled off shows the failure of friction test.

Following the carrying out of sonicated test in methyl alcohol (or other solvent that is fit to, for example isopropyl alcohol).For example, Tinted contact lenses immersed in the methyl alcohol of 5ml or isopropyl alcohol or the suitable solvent carried out sonicated about 1 minute, put into the phial that BBS (BBS) is housed then.After about 10 seconds, emit salt solution, add the fresh BBS of about 5ml.Balance is after about 5 minutes among the BBS, and the adhesiveness of checking lens is destroyed sign (for example colouring agent bleeding, stain or peel off).

Those skilled in the art are well-known, and the mould that is used for molding valve calotte can be an assembly or cup-shaped.The mould that is used for molding valve calotte is preferably made with plastic material.Preferably with at least a portion of mould molding face with mode preliminary treatment well-known in the art to increase its hydrophily or wetability.For example, the mould molding face at least partly or entirely before it uses, stand sided corona treatment, preferentially adhere to the forming surface that is used for following process (for example cutting) for use in the valve calotte (or the molded lens blank of single face) of molding.Mould how to make molded polymeric valve calotte (or the molded lens blank of single face) that be used to cast as well known to those skilled in the art.Should be understood that the optics finished surface facing surfaces with the valve calotte can be flat or crooked, preferably convex half-sphere shape surface.

In preferred embodiments, first forming surface with optical quality of first half module limits the rear surface of the contact lenses that will make.Only one side of lens (front surface) and rims of the lens need cut on the valve calotte.

Should be understood that and well known to a person skilled in the art that rotated mold filing can be used for producing the valve calotte.Making by rotated mold filing in the process of valve calotte, with lens-forming material be put into have optics concave surface (forming surface) by in the wetting die cavity of described material, then one next forced feed is to the arrival end of rotation polymerization post intermittently, it is regional and towards the polymerisation zone of the port of export that it is included near the arrival end " adjustings " ideally.Preferred this mold feature is with means preliminary treatment optical surface well known in the art to increase its hydrophily or wetability.When being fixed on the concerning of interference fit (interference fitting), pipe and the rotational speed regulation of mould to causing and/or keeping lens-forming material radially outward to transfer to predetermined lens textural, will be formed the contact lenses of required form under its polymerizing condition that uses in pipe.For example, can use 300r.p.m. and lower easily to 600r.p.m. and higher rotating speed.Certainly, the precise rotation that uses in the operation is in experienced operator's technical scope.The factor of considering comprises the type of each component of the lens-forming material that contains use and concentration, the operating condition of selection, the type and the concentration of initator, and/or the energy source strength and the type of initiated polymerization, and the factor of these discussion is can predict and conspicuous to the experienced operator.

Those skilled in the art are well-known must to be to be made by the material that does not hinder actinic radiation to be transmitted into the zone of convergency of this post as the polymerization post (pipe) that typically is used for rotated mold filing.When using long wavelength U.V. light as actinic radiation, glass will be the material that is suitable for this polymerization post as PYREX.During other actinic radiation type of enumerating more than using, the polymerization post can be by manufacturings such as various types of metals such as steel, nickel, bronze, various alloys.

According to the present invention, can printing ink be applied on the forming surface of mould according to any printing technology such as intaglio plate transfer printing (or intaglio plate bat printing) or ink jet type printing.The printing technology that should be understood that other type also can be used for graphic arts die.

In the intaglio plate transfer printing, coloured image is put in or prints on the intaglio plate transfer device, and with the image transfer on the transfer device to another surface, as (the U.S. Patent No. 3 of Spivack on polymer or the lens, 536,386,4,582 of Knapp, 402 and 4,704,017; People such as Rawlings 5,034,166).It below is the representative instance of this printing.Image is etched into metal forms block.This block is put in the printer.In case in printer, block slips over image by open inkwell wiping system or closed printing ink inking hole and inking.Then, the siloxanes intaglio plate from block gather ink image and with this image transfer to contact lenses.This siloxanes intaglio plate is made by the material of the elastic variable that contains siloxanes.The characteristic of silicone compositions allows that printing ink water temporarily is adhered on the intaglio plate, and discharges from intaglio plate fully when it contacts with contact lenses or mould.Suitable intaglio plate transfer printing structure include, but not limited to Tampo type print structure (Tampo vario 90/130), rubber impression, sleeve pipe, doctor, directly printing or this area is public and transfer printing.

The printing ink that is used for the intaglio plate transfer operation preferably has one or more following features: viscosity is lower than about 50,000cps, preferably be lower than about 5000cps and most preferably be lower than 1500cps, granularity is lower than about 5 microns (for non-pearlescent pigments), the about 20 mN/m-60 mN/m of surface tension; Long-time stability (that is: stablized about 4 hours, preferably at least 8 hours, more preferably 24 hours, more preferably at least 7 days, at least three weeks most preferably); Suitable color level (eyes as seen); Good adhesion to medical apparatus; With by the good transfer of mould to the medical apparatus that in mould, makes.The physical stability of printing ink can be different from its chemical stability.For example, pigment can sedimentation in printing ink (physical phenomenon), yet printing ink does not carry out any tangible chemical reaction.For this type of situation, printing ink can be by simple stirring or is mixed and return to upstate.The alternate manner that slows down or eliminate pigment precipitation includes, but not limited to use additive, changes pH, on-line mixing, refrigeration, change pigment granularity and coating granules of pigments pigment (coating pigment of pigment particles).

Use ink jet printing method printing lens to be described among the disclosed US patent application No.2001/0050753,2001/0085934,2003/0119943 and 2003/0184710.

Apply for ink-jet, printing ink of the present invention has one or more following features: viscosity is lower than about 50 centipoises (cps), preferably is lower than about 15cps; Most preferably be lower than 15cps; Surface tension is about 20mN/m-60 mN/m; Granularity is lower than about 5 microns; Long-time stability (promptly stablized about 4 hours, preferably at least 8 hours, more preferably at least 24 hours, more preferably at least 7 days, at least three weeks most preferably); Suitable color level (eyes as seen); Uniform water droplet form (promptly not having " coffee dyeing " or " annular " effect); Jetting stability (promptly forming single water droplet easily); Good adhesion to medical apparatus; By the good transfer of mould to the medical apparatus that in mould, makes; And the stability (minimum drying or skinning effect) of printing ink in inkjet nozzle.

" coffee dyeing outward appearance " used herein or " coffee coloration " meaning is the interior zone that the color dot on contact lenses or the mould has dark periphery and light color.

" annular appearance " used herein or " annular effect " meaning is that the color dot on contact lenses or the mould has by circumjacent light color of the annular region of dark color or colourless central area.

According to the present invention, well known to a person skilled in the art that any ink solidification method can be used for the present invention.The example of ink solidification method includes, but not limited to heat cure, photochemical curing (promptly solidifying by actinic radiation), humidification curing, passes through to use chemical method, and for example necleophilic reaction or oxidation reaction are solidified.

According to the present invention, it can be solution or solvent-free liquid or the melt under the temperature below 60 ℃ that lens form fluent material.According to the present invention, it can be any preparaton that is used to make soft contact lenses that lens form fluent material.Exemplary preparaton includes, but not limited to lotrafilcon A, lotrafilcon B, etafilcon A, genfilcon A, lenefilcon, polymacon, acquafilconA and balafilcon.

Wherein to form fluent material be solution to lens, the vinyl monomer that it can be by will at least aly containing siloxanes or monomer and at least a hydrophilic ethylene monomer and all other required components dissolved in well known to a person skilled in the art any suitable solvent (for example comprise aforesaid those) prepare greatly.

According to the present invention, any known suitable siloxane macromonomers that contains, for example above disclosed those, can be used for preparing soft contact lenses.Any known suitable siloxanes vinyl monomer that contains, for example above disclosed those, can be used for preparing soft contact lenses.

The example of the hydrophilic monomer that is fit to be aforesaid those.

In preferred embodiments, lens-forming material is the composition that can form siloxanes aquogel, and this hydrogel has the room temperature machinability, promptly has about 25 ℃ or higher main glass transition temperature (T _g).

In a more preferred embodiment, lens-forming material is the U.S. patent application No.60/583 that is disclosed in the common transfer of submitting on June 30th, 2004, the solvent-free polymerisable compound (herein being incorporated herein by reference) in 994.This type of solvent-free polymerisable compound comprises (a) at least a vinyl monomer or big monomer or their mixture that contains siloxanes, (b) at least a hydrophilic ethylene monomer and (c) at least a consumption be enough to dissolve the hydrophily in the polymerisable compound and the mediation vinyl monomer of hydrophobic components.

" be in harmonious proportion (blending) vinyl monomer " refers to the hydrophily that not only can be used as the dissolution with solvents lens-forming material and hydrophobic components but also can be used as one of polymerizable components and carry out the vinyl monomer that polymerization forms the siloxanes aquogel material.Preferred mediation vinyl monomer is present in the lens-forming material with the amount of about 5-30 weight %.

Can use the hydrophily that to dissolve in the lens-forming material and hydrophobic components to form any suitable vinyl monomer of solution.The vinyl monomer preferred examples that is in harmonious proportion includes, but not limited to aromatic vinyl monomer, contains the vinyl monomer of cycloalkyl.These preferred blend monomers can improve the main glass transition temperature that contains the siloxanes aquogel material that the polymerisable compound of these preferred blend monomers prepares by curing.

The example of preferred aromatic vinyl monomer comprises styrene, 2,4,6-trimethylbenzene ethene (TMS), t-butyl styrene (TBS), 2,3,4,5,6-phenyl-pentafluoride ethene, methacrylic acid benzyl ester, divinylbenzene and 2-vinyl naphthalene.In these monomers, it is preferred containing cinnamic monomer.To contain cinnamic monomer here and be defined as and contain the monomer that directly is keyed to the vinyl group on the phenyl, wherein phenyl can be substituted (except being replaced by condensed ring), for example, uses 1-3 C as mentioned above ₁-C ₆Alkyl replaces.Styrene [H itself ₂C=CH-C ₆H ₅] be the particularly preferred cinnamic monomer that contains.

The vinyl monomer that will contain cycloalkyl here is defined as and contains by 3 C at the most ₁-C ₆The cycloalkyl vinyl monomer that alkyl replaces.Preferably contain acrylate and methacrylate that the cycloalkyl vinyl monomer includes, but not limited to contain separately cyclopenta or cyclohexyl or suberyl, they can be by 3 C at the most ₁-C ₆Alkyl replaces.Preferably contain cycloalkyl vinyl monomer example and comprise isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate etc.

Lens-forming material preferably comprises one or more T in addition _gThe vinyl monomer that improves, this vinyl monomer is selected from by acrylic acid, methacrylic acid C ₁-C ₄Arrcostab (for example methyl methacrylate, EMA, propyl methacrylate, isopropyl methacrylate, metering system tert-butyl acrylate), methacrylonitrile, acrylonitrile, acrylic acid C ₁-C ₄The group that Arrcostab, N-N-isopropylacrylamide, 2-vinylpyridine and 4-vinylpridine are formed.The vinyl monomer that should be understood that aromatic monomer and/or contain cycloalkyl can be substituted by the vinyl monomer that one or more above-mentioned Tg improve.

According to the present invention, lens-forming material can comprise various components in addition, as crosslinking agent, hydrophobicity vinyl monomer, initator, UV-absorbent, inhibitor, filler, observability toner, antimicrobial etc.

Crosslinking agent can be used to improve structural intergrity and mechanical strength.The example of crosslinking agent comprises, but be not limited to, (methyl) acrylic acid allyl ester, two (methyl) acrylic acid low-grade alkylidene diol ester, poly-low-grade alkylidene glycol two (methyl) acrylate, two (methyl) acrylic acid low-grade alkylidene ester, divinyl ether, divinylsulfone, two-or trivinylbenzene, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, bisphenol-A two (methyl) acrylate, di-2-ethylhexylphosphine oxide (methyl) acrylamide, phthalic acid triallyl ester or diallyl phthalate.Preferred cross-linking agents is GDMA (EGDMA).

The amount of the crosslinking agent that uses represents that with the weight content with respect to total polymer this amount is 0.05-20%, especially 0.1-10%, and is preferably 0.1-2%.If crosslinking agent is the block copolymer of dimethyl silicone polymer or dimethyl silicone polymer, its percetage by weight in preparaton can be 30-50%, because the existence of this type of material can improve oxygen permeability.

For example, be selected from the known initator that is used for the material of this type of polymerization field, can be included in lens and form in the fluent material, so that promote and/or improve polymerization rate.

The light trigger that is fit to is benzoin methyl ether, diethoxy acetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenylketone and Darocur and lrgacur type, preferred Darocur 1173  and Darocur 2959 .The example of benzoyl phosphine initator comprises 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; Two-(2,6-dichloro-benzoyl base)-4-N-propyl group phenylphosphine oxide; With two-(2,6-dichloro-benzoyl base)-4-N-butyl phenyl phosphine oxide.For example, can introduce big monomer or can be used as the reactive photoinitiators that particular monomers uses and also be fit to.The example of reactive photoinitiators is to be disclosed among the EP 632 329 those.Thereby polymerization can be by actinic radiation, light for example, and the UV that especially is fit to wavelength is light-initiated.If therefore suitable, spectrum requires and can control by adding suitable sensitising agent.

The thermal initiator example that is fit to includes, but not limited to 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile), peroxide such as benzoyl peroxide etc.Preferred thermal initiator is azodiisobutyronitrile (AIBN).

The present invention is not limited to any specific mechanism or theory, it is believed that coloured film is fixed in the lens blank by encapsulation and/or interpenetrating polymer networks formation.By allowing that before curing the coloured film with coloured image is soaked in the lens formulation, people can obtain lens blank, and wherein the same forming surface of this printing image (antecurvature or the back of the body arc) flushes or is lower than this forming surface.The degree of depth of image in lens blank of printing will depend on the surface characteristics (for example corona is for non-sided corona treatment surface) of soak time, temperature, lens formulation, ink formulations and one-side mould assembly and the density of possible printing image equally.Coloured film preferably uses lens-forming material to soak more preferably at least 10 minutes and more preferably at least 20 minutes at least 5 minutes.

Lens-forming material solidifies and can heat cause or photochemical initiation.

Solidify the back and/or dry step is preferably at high temperature carried out, and for example carries out under about 75 ℃ or higher temperature.Solidify the back and/or drying steps by carrying out, and thinks in the valve calotte the further polymerization and can remove solvent (if you are using) of residual unconverted monomer and/or big monomer.Thereby the increase of the hardness of resulting polymers, thereby realized resulting polymers machinability at room temperature.By the drying of under the high temperature decompression, carrying out resulting polymers it is further facilitated.

Only add in the fluent material at high temperature (promptly solidifying to form the temperature more than the solidification temperature in the step of the valve calotte) high-temperature initiator of activation down by forming at lens, the back curing of resulting polymers also can be more convenient.In back curing and/or drying steps process, add high-temperature initiator by forming in the fluent material at lens, can make the complete polymerization of any remaining polymerizable components that stays after the curing schedule, to increase the hardness of the gained siloxanes aquogel material that will cut.In addition, high-temperature initiator also can be in order to increase crosslink density and hardness in back curing and/or drying steps.The example of the high-temperature initiator that is fit to comprises, but be not limited to, available from the VAZO-88,2 of Dupont, two (tert-butyl peroxide)-2 of 5-, 5-dimethylhexane, benzoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, t-butyl hydroperoxide and the peracetic acid tert-butyl ester.

The cutting of preferred valve calotte is at room temperature carried out.Any known suitable topping machanism can be used for the present invention.Preferably can be computer-controlled (or numerical control) cutting be used for the present invention.The numerical control twin shaft cutter that more preferably will have the cutting of 45 ° of piezoelectricity, or by Durazo and Morgan at US patent No.6, disclosed topping machanism is used for the present invention in 122,999.Exemplary preferred topping machanism comprises, but be not limited to, available from Precitech, the numerical control cutting machine of Inc., for example, the Optoform ultra precision cutting machine (model 30,40,50 and 80) that has the piezoelectric ceramics fast response servo annex (fast tool servo attachment) of various ways.

The present invention allow have that the printing image is positioned on the lens surface or under MTO or the silicone hydrogel lens of customization produce by cutting at room temperature.Colored silicone hydrogel lens produced according to the invention are worn lens and are worn lens for a long time as daily.These lens make it possible to change or strengthen patient's eye color.This can finish with one or more printing images on the lens.The printing ink that is used to print can be transparent or opaque.In addition, these lens can also be used as the compensating lens.Be used for the printing framing is compared with the method on being printed on lens surface in the method under the lens surface and improved comfortableness.The present invention will make people the lens blank of printing can be cut into the design of any required prescription or lens.The silicone hydrogel lens blank of printing can be cut into lens with common cutting apparatus (promptly not comprising cryogenic technique), the parameter (common or extreme parameter) and the lens that make the colored silicone hydrogel lens can obtain extensively to change design (for example anchor ring, bifocal).

Should be understood that method of the present invention can be used for producing respirable impermanent body art.For example people can be imparted to the image of wanting on the silicone copolymers, then this image are fixed on the person.This type of body art comprises with some advantages of comparing of forever tatooing, for example, if want to remove than being easier to, favorable durability, good oxygen permeability/respiration capability, covering the ability of scar or the damage of other outward appearance.

The printing ink that should be understood that any known manufacturing non-silicone hydrogel lens also can be used for the present invention's (but not being preferred).

Aspect different, the invention provides the method for making colored silicone hydrogel contact lenses, this method comprises: the mould that is provided for valve calotte casting molding, wherein this mould comprises the forming surface with optical quality, and wherein this forming surface limits one of them of silicone hydrogel contact lenses rear surface and front surface; Apply color coat at least a portion of mould molding face with printing ink, wherein this printing ink comprises at least a colouring agent and polymer adhesive, and wherein this binder polymer comprises the segment that derives from least a hydrophilic ethylene monomer or big monomer; Randomly solidify this color coat and be attached to coloured film on this forming surface to form not with covalent manner; Form fluent material with the lens that comprise at least a vinyl monomer that contains siloxanes or big monomer and at least a hydrophilic ethylene monomer and be full of mould; In mould, solidify this lens-forming material, formation has the valve calotte corresponding to the forming surface of one of them of contact lenses front surface and rear surface, wherein this valve calotte comprises and being fixed in wherein and/or color coat on it or film, and wherein the forming surface of this valve calotte comprises at least a portion of color coat or film; Remove this valve calotte by mould; With solidify behind this valve calotte and/or dry sufficiently long a period of time to improve this valve calotte machinability at room temperature; And form front surface or rear surface by on the side relative, directly cutting this valve calotte, obtain colored silicone hydrogel contact lenses thus with forming surface.

According to the present invention, the binder polymer in the printing ink should comprise crosslinkable groups, and this group is selected from that (wherein R is hydrogen or C by ethylenically unsaturated group, hydroxyl-OH, amino-NHR ₁-C ₈Alkyl), carboxylic acid-COOH, epoxy, acid amides-CONHR, isocyanates, peroxide, perester, acid anhydrides, alkoxy silane, silanol, acetoxylsilane, silane, halosilanes and their group in conjunction with composition.

Preferably the color coat on the mould molding face is solidified to form coloured film.

Previous disclosed content will make the personnel with ordinary skill can put into practice the present invention.In order to make the reader understand specific embodiment and advantage thereof better, suggestion is with reference to the following example.Percentage in the preparaton is based on percetage by weight, unless otherwise mentioned.

Embodiment 1

This embodiment describes the synthetic of synthesizing of photocurable binder polymer precursor and photocurable binder polymer.

Synthetic siloxane-containing copolymer with side chain functionalities

The solution of in 1 liter jacketed glass still, packing into and forming by VAZO-64 (0.6472g), DMA (106.09g), TRIS (106.26g), mercaptoethanol (0.253g), HEMA (37.55g) and ethyl acetate (301.9g).At room temperature with nitrogen bubble by about 15 minutes of this mixture, then mixture is heated to 40 ℃ and stir with about 200 RPM.After about 16 hours, it is more tacky that reactant mixture obviously becomes.Reaction is analyzed by FT-IR and is monitored.Behind about 20 hours total reaction time, will add in the reactant mixture by the solution that 11mg 4-hydroxyl-TEMPO (4-hydroxyl-2,2,6,6-tetramethyl piperidine oxygen base, free radical) and 2.38 gram ethyl acetate are formed.The gravimetric analysis of reactant mixture shows that solution has about 68% solids content.FT-IR analyzes: will several reactant mixtures place the hexane of about 15ml, the precipitation of generation is separated from hexane and it is dissolved in the absolute ethanol.Casting film on the NaCl disk, and in about 5 minutes of 75 ℃ of dryings (or 100 ℃ of dryings about 10 minutes).The characteristic peak that monitors acid amides and ester and hydroxy functional group is respectively 1643.7 and 1724.4cm ^-1

Prepare photocurable binder polymer

In the solution of siloxane-containing copolymer (precursor of above preparation) in ethyl acetate of 150.17g 68%, add in the solution of forming by 18.8029g methacrylic acid 2-isocyanato ethyl (IEM) and 0.0035g4-hydroxyl-TEMPO.At room temperature stir this mixture up to evenly with spatula, detect by FT-IR then.Dibutyl tin laurate (DBTDL) with 0.0705g stirs in this reactant mixture of adding then.About 45 minutes of 35 ℃ of heating, FT-IR detected and shows that this moment, NCO no longer existed with reactant mixture.

Embodiment 2 (the synthetic big monomer that contains siloxanes)

Be 1030g/mol with 51.5g (50mmol) mean molecule quantity and (, Milan) introduce in the there-necked flask with the 50mg dibutyl tin dilaurate available from Ausimont S.p.A according to the PFPE Fomblin  ZDOL that end group titration contains 1.96 milliequivalents (meq)/g hydroxyl.Flask contents under agitation is evacuated down to about 20 millibars, then reduces pressure with argon gas.This operation repeats twice.The isoflurane chalcone diisocyanate that subsequently 22.2g (0.1mol) is stored in the new distillation under the argon gas adds under the argon gas adverse current.Temperature in the flask remains on below 30 ℃ by the water-bath cooling.After stirring was spent the night under the room temperature, reaction was finished.The isocyanates titration obtains 1.40meq/g NCO content: (theory: 1.35 meq/g).

Is the α of 2000 g/mol with 202g available from Shin-Etsu, mean molecule quantity, and ω-hydroxypropyl terminated dimethyl silicone polymer KF-6001 (is 1.00meq/g according to the titration hydroxyl) introduces flask.Flask contents is evacuated to about 0.1 millibar and reduce pressure with argon gas.This operation repeats twice.The siloxanes of the degassing is dissolved in 202ml is stored in new distillation toluene argon gas under adding 100mg dibutyl tin dilaurate (DBTDL).After the complete homogenizing of solution, under argon gas, add all the PFPE that reacts with isoflurane chalcone diisocyanate (IPDI).After stirring was spent the night under the room temperature, reaction was finished.Solvent is removed in the room temperature stripping under high vacuum.Microtitration shows the hydroxyl (theoretical 0.37meq/g) of 0.36meq/g.

The methacrylic acid 2-isocyanato ethyl (IEM) of 13.78g (88.9mmol) is joined 247g α under argon gas, in polysiloxanes-PFPE-polysiloxanes triblock copolymer of σ-hydroxypropyl terminated (triblock copolymer that stoichiometry is average, but also have other block length).Mixture was at room temperature stirred three days.Microtitration no longer shows and has any NCO (detectable limit is 0.01 meq/g) then.Find the methacryl (the theoretical 0.34meq/g of being) of 0.34 meq/g.

Zhi Bei big monomer is fully colourless and transparent like this.It can be under no optical condition in air in the room temperature storage several months, and molecular weight is without any variation.

Embodiment 3

But big monomer, TRIS, t-butyl styrene and the VAZO-52 of DMA, embodiment 2 preparations are mixed to prepare the solvent-free preparaton that as shown in table 1 being used to prepares the siloxanes aquogel material of room temperature cutting.With t-butyl styrene join in this preparaton with guarantee all components under the situation of solvent-free (for example ethanol) miscibility and improve the cutting characteristic (T of increase of polymer _g).

Table 1

Component	Preparaton (weight %)
		DMA	33.72
Betacon	37.91
		TRIS	18.12
T-butyl styrene	9.99
		VAZO-52	0.253

^*Preparation among the embodiment 2

Embodiment 4

Photocurable printing ink prepares by mixing 22.64 gram binder polymer A and 1.38 gram PCN-0.0581 gram Irgacure 2959 green and that be dissolved in the 1.5 gram ethyl acetate.This printing ink is at 25 ℃ of brookfield viscosities with about 680cps.

Embodiment 5

The lens blank (or valve calotte) of printing is prepared as follows:

Photocurable siloxanes aquogel printing ink with embodiment 4 preparations makes the stereotype inking, and the silicon rubber printing gravure is used for iris shape image is transferred on polypropylene convex (basic arc) half module (FreshLook ).This base arc half module carries out sided corona treatment (33 dyne) before printing.Then half module being placed in the UV that high portion is fixed with the UV-B lamp solidifies in the case (UV-cure box) (Phillips TL 40 W/12 RS).With sample with UV-B light from about 90 minutes (intensity～3.6mW/cm of top radiation ²).Solidify the case bottom and be fixed with 40 watts of F40BL lamps of Phillips.The basic arc half module of the printing ink that will print and solidify is put into the plastics inking hole of the silicone hydrogel lens preparaton that about 0.75ml embodiment 3 preparations are housed then.Base arc half module is by interlayer die assembly (being made up of protruding half module and the plastics inking hole) levelling between two flat, plastic sheets.After about 30 minutes soak times, die assembly places the pressurized air baking oven, and with the heat cure of lens polymerization thing.The program curing that uses provides in table 2.

Table 2

Rise (Ramp)	Solidification temperature/hardening time
		Rose 10 minutes from 45 ℃ set points	75 ℃/2 hours
Rose 10 minutes from 75 ℃	110 ℃/1 hour
Solidify the back	Back solidification temperature/rear curing time
		Baking oven is preheating to 110 ℃	110 ℃/16 hours
Remarks: basic arc mould removes in plastics inking hole before the curing operation of back.

After the curing, obtain the printing lens blank on polypropylene-base arc mould.Lens blank is removed and analyzes on polypropylene-base arc mould.Inspection to lens blank shows printed patterns (being that printed patterns is embedded in this lens blank) below the basic cambered surface of lens blank molding.By checking cross-section lens blank, very clearly find out that printed patterns is below the basic cambered surface of lens blank molding.

The differential scanning calorimetry of the polymer sheet that downcuts on lens blank (DSC) analysis shows, the glass transformation temperature (T of polymer _g) about 63 ℃ (scanning for the second time, 20 ℃/minute the rate of heat addition).Obviously, this material is glass and based on the machinable at room temperature of its glass transition temperature.

Claims (20)

1. method of making colored silicone hydrogel contact lenses, it may further comprise the steps:

(a) be provided for the mould of molding valve calotte, wherein this mould comprises the forming surface with optical quality, and wherein this forming surface limits one of them of silicone hydrogel contact lenses rear surface and front surface;

(b) with on printing ink at least a portion with color coat paint mould molding face, wherein this printing ink comprises at least a colouring agent and the polymer adhesive that contains siloxanes;

(c) solidify this color coat and form coloured film, this film contacts with forming surface but is not attached on this forming surface with covalent manner;

(d) form fluent material with the lens that comprise at least a vinyl monomer that contains siloxanes or big monomer and at least a hydrophilic ethylene monomer and fill this mould;

(e) make lens-forming material soak the sufficiently long time of this coloured film, make a part of lens-forming material penetrate into the space between coloured film and the forming surface, simultaneously partially or completely by separating this coloured film on the forming surface;

(f) solidify this lens-forming material in mould, form and have corresponding to one of them the valve calotte of forming surface of contact lenses front surface and rear surface, wherein this valve calotte comprises and being fixed in wherein and/or the coloured film on it;

(g) remove this valve calotte from mould; With solidify behind this valve calotte and/or the dry sufficiently long time to improve this valve calotte machinability at room temperature; With

(h) directly cut the valve calotte in the relative side of this forming surface, form front surface or rear surface.

2. method according to claim 1, the binder polymer that wherein contains siloxanes comprises crosslinkable groups, and this group is selected from that (wherein R is hydrogen or C by ethylenically unsaturated group, hydroxyl-OH, amino-NHR ₁-C ₈Alkyl), carboxylic acid-COOH, epoxy, acid amides-CONHR, isocyanates, peroxide, perester, acid anhydrides, alkoxy silane, silanol, acetoxylsilane, silane, halosilanes and their group in conjunction with composition.

3. method according to claim 2, the binder polymer that wherein contains siloxanes comprises ethylenically unsaturated group.

4. method according to claim 3, wherein step (c) is undertaken by heating or actinic radiation.

5. method according to claim 2, the binder polymer that wherein contains siloxanes comprises the side chain crosslinkable groups, and this group is selected from the group of being made up of alkoxysilane group, silanol group, acetoxylsilane base, silylation, halosilanes base and their combination.

6. method according to claim 5, wherein step (c) is undertaken by humidification activation.

7. method according to claim 2, the binder polymer that wherein contains siloxanes comprises crosslinkable groups, and this group is selected from that (wherein R is hydrogen or C by hydroxyl-OH, amino-NHR ₁-C ₈Alkyl), carboxyl-COOH, epoxy radicals, amide groups-CONHR and their group in conjunction with composition.

8. method according to claim 2 is wherein carried out preliminary treatment to improve its hydrophily or wetability at least a portion of mould molding face.

9. method according to claim 2, wherein lens-forming material is can form to have about 25 ℃ or higher main glass transition temperature (T _g) the composition of siloxanes aquogel.

10. method according to claim 9, wherein step (h) is at room temperature carried out.

11. method according to claim 2, wherein this coloured film was soaked about 5-30 minute by lens-forming material.

12. a method of making colored silicone hydrogel contact lenses, it may further comprise the steps:

(a) be provided for the mould of valve calotte casting molding, wherein this mould comprises the forming surface with optical quality, and wherein this forming surface limits one of them of silicone hydrogel contact lenses rear surface and front surface;

(b) with on printing ink at least a portion with color coat paint mould molding face, wherein printing ink this comprise at least a colouring agent and polymer adhesive, wherein this binder polymer comprises the segment that derives from least a hydrophilic ethylene monomer or big monomer;

(c) randomly solidify this color coat and be attached to coloured film on the forming surface to form not with covalent manner;

(d) form fluent material with the lens that comprise at least a vinyl monomer that contains siloxanes or big monomer and at least a hydrophilic ethylene monomer and fill this mould;

(e) in mould, solidify this lens-forming material, formation has corresponding to one of them the valve calotte of forming surface of contact lenses front surface and rear surface, wherein this valve calotte comprises and being fixed in wherein and/or color coat on it or film, and wherein the forming surface of this valve calotte comprises at least a portion of color coat or film; Remove this valve calotte by mould;

(f) with solidify behind this valve calotte and/or dry sufficiently long a period of time to improve this valve calotte machinability at room temperature; With

(g) by on the relative side of this forming surface, directly cutting this valve calotte to form front surface or rear surface.

13. method according to claim 12, wherein binder polymer comprises crosslinkable groups, and this group is selected from that (wherein R is hydrogen or C by ethylenically unsaturated group, hydroxyl-OH, amino-NHR ₁-C ₈Alkyl), carboxylic acid-COOH, epoxy, acid amides-CONHR, isocyanates, peroxide, perester, acid anhydrides, alkoxy silane, silanol, acetoxylsilane, silane, halosilanes and their group in conjunction with composition.

14. method according to claim 12, wherein binder polymer comprises the segment that derives from least a vinyl monomer that contains siloxanes or big monomer.

15. method according to claim 14, the binder polymer that wherein contains siloxanes comprises ethylenically unsaturated group.

16. method according to claim 14, the binder polymer that wherein contains siloxanes comprises the side chain crosslinkable groups, and this group is selected from free alkoxysilane group, silanol group, acetoxylsilane base, silylation, halosilanes base and their group in conjunction with composition.

17. method according to claim 12 is wherein carried out preliminary treatment to improve its hydrophily or wetability at least a portion of mould molding face.

18. method according to claim 12, wherein lens-forming material is can form to have about 25 ℃ or higher main glass transition temperature (T _g) the composition of siloxanes aquogel.

19. method according to claim 18, wherein step (h) is at room temperature carried out.

20. method according to claim 14, in step (d) with (e), further comprise coloured film is soaked the sufficiently long time, make a part of lens-forming material penetrate into the space between coloured film and the forming surface, on forming surface, separate the step of this coloured film simultaneously partially or completely.